Alkylthiosulfenyl dithiocarbamates and their preparation



Patented Sept. 28, 1954 2 69@ 440 UNITED STATES ATENT OFFICE ALKYLTHIOSULFENYL DITHI OCARBAM- ATES AND THEIR PREPARATION Chester M. Himel, Menlo Park, Calif., and Lee 0. Edmonds, Bartlesville, kla., assignors to Phillips Petroleum (lompany, a corporation of Delaware N 0 Drawing. Application October 29, 1951, Serial N0. 253,765

23 Claims. (Cl. 260247.1) 1 2 This invention relates to new compositions and of our invention are those having a composition their manufacture. In one aspect this invention in accordance with the following structural relates to alkylthiosulfenyl dithiocarbamates and formula:

their preparation. application is a continu- R ation-in-part of our copending application Serial 5 Number 59,025, filed November 8, 1948, now N G SM Patent No. 2,572,845. R/

An object of our invention is to provide alkylthiosulfenyl dithiocarbamates as new compositions. Another object is to provide a process for the manufacture of alkylthiosulfenyl dithiocarbamates. Other objects will be apparent to one skilled in the art from accompanying discussion and disclosure.

In accordance with our invention we provide new and novel chemical compounds, alkylthiosulfenyl dithiocarbamates, having a composition in accordance with the following structural formula:

wherein each R is selected from the group consisting of aryl, aralkyl and alkaryl radicals containing not more than 10 carbon atoms, and radicals which together with the nitrogen form a heterocyclic ring, wherein one B can also be a radical selected from the group consisting of hydrogen, and an alkyl containing not more than 10 carbon atoms, and wherein M is selected from the group consisting of alkali metals and alkaline earth metals.

The alkylthiosulfenyl halides employed in this invention are compounds having the general formula: RSS--X wherein R is selected I from the group consisting of primary, secondary and tertiary alkyl radicals containing not more R than 10 carbon atoms and wherein X is selected wherein each R is selected from the group con- 5 from the group consisting of chlorine, bromine sisting of aryl, aralkyl and alkaryl radicals, conand iodine. taining not more than 10 carbon atoms, and When employing an organic solvent in the inradicals which together with the nitrogen form a troduction of the alkyl-thiosulfenyl halide to the heterocyclic ring, wherein one R, can also be a reaction as already described, we prefer as such radical selected from the group consisting of a solvent any low-boiling saturated hydrocarbon hydrogen, and an alkyl containing not more than such as normal pentane, isopentane, light satu- 10 carbon atoms, and wherein R is selected from rated naphthas, mixtures of low-boiling inert the group consisting of primary, secondary and hydrocarbons, and the like, boiling in the range tertiary alkyl radicals containing not more than of 10 to 60 0., although higher boiling solvents 10 carbon atoms. In our preferred compositions may be advantageously employed in some cases,

containing the heterocyclic ring, the said heteroas Where higher molecular weight reactants are cyclic ring is saturated and contains from 5-7 employed. We often prefer to dissolve the alkylatoms selected from the group consisting of carthiosulfenyl halide in the selected organic solvent, bon, nitrogen, sulfur, and oxygen, at least one in an amount of from 0.25 to 2 moles per liter of of which is the said N set forth in the structural solvent. Temperatures most usually applicable formula hereinabove, and at least three of which to the practice of our invention are within the are carbon. Our preferred process for producing range of from about l0 to 60 (3., although more the compounds of our invention is from the intergenerally we prefer to operate in a range of from action of alkylthiosulfenyl halides with the salts 19 to 426 C. Pressures are generally atmospheric of N-substituted dithiocarbamic acids. These 5 although higher pressures may be employed, if products have numerous potential uses, such as desired. In general, it is preferable to conduct rubber vulcanization accelerators, fungicides, the reaction in a vessel with a reflux condenser. intermediates for the production of valuable or- By so operating the temperature is easily conganic chemicals, and the like. trolled at a desired level, and also a convenient In the practice, of a preferred embodiment of means of agitation for the system is thereby proour invention we prepare our new compositions vided, by the ebullition of the low-boiling inert by slowly adding an alkylthiosulfenyl halide, solvent. It is to be understood that it is Within preferably in solution in a chemically inert orthe scope of our invention to conduct the prodganic solvent, to an aqueous solution of a suitable net-forming step of our process in the absence of salt of an N-substituted dithiocarbamic acid, the an inert organic solvent, and that we employ this system being well agitated during the addition. solvent as a means for controlling the reaction, to The resulting reaction mixture is then stirred proceed at a rate conducive to producing optiusually from 3 to 10 minutes after which the mum yields of desired product, in view of the product is recovered. highly active nature of the alkylthiosulfenyl The dithiocarbamates employed in the practice 50 halides.

In another embodiment of our invention we may prepare our new compounds in a single inert solvent medium utilizing a solvent of the type already described. In the practice of this embodiment the reactants may be introduced to the reaction system in any desired manner. For example, solid N-substituted dithiocarbamate may be introduced to an alkylthiosulfenyl halide in solution in the inert organic solvent in a desired proportion, at any desired rate, or the halide in solution in the inert organic solvent may be introduced to the N -substituted dithiocarbamate when suspended in another portion of the same organic solvent.

We prefer to employ equimolar proportions of reactants in our process, although if desired, an excess of reactant may be used.

Examples of the compositions provided in accordance with our invention are:

N-phenyl-Stertbutylthiosu1fenyl dithiocarbamate N,N-dipheny1-S-n-propylthiosulfeny1 dithiocarbamate N-benzyl-S-heptylthiosulfenyl dithiocarbamate N-beta-phenylethyl-S-octylthiosulfenyl dithiocarbamate N-gamma dithiocarbamate N beta phenylethyl N methyl S n propylthiosulfenyl dithiocarbamate N-beta-phenylbutyl-S-tert-butylthiosulfenyl dithiocarbamate N gamma naphthylpropyl-S-tert-butylthiosulfenyl dithiocarbamate N-benzyl-N-pentyl-S-n-propylthiosulfenyl thiocarbamate N,N-ditolyl-S-nbutylthiosulfeny1 dithiocarbamate N-xylyl-S-hexylthiosulfenyl dithiocarbamate N- (diethylphenyl) -S-octylthiosu1fenyl carbamate N (para dimethylphenyl) S tert butylthiosulfenyl dithiocarbarnate N-ethylphenyLN-n-butyl-S tert butylthiosulsulfenyl dithiocarbamate N-benzyl-N-methyl-S-tert-butylthiosulfenyl dithiocarbamate Pentamethylene-S-tert-butylthiosulfeny1 dithio- Examples of the i i-substituted dithiocarbamate salts employed as reactants in accordance with the process of our invention are:

Sodium N-phenyl-N-methyl dithiocarbamate phenylpropyl S pentylthiosulfenyl dithio- Examples of alkyl thiosulfenyl halides employed as reactants in the process of our invention are:

n-Butylthiosulfenyl chloride Tert-butylthiosulfenyl chloride i-Propylthiosulienyl bromide Hexylthiosulfenyl iodide Octylthiosulfenyl bromide Decylthiosulfenyl chloride i-Pentylthiosulfenyl chloride Methylthiosulfenyl bromide n-Propylthiosulfenyl chloride Our invention is illustrated by the following examples. The reactants, their proportions, and other specific ingredients are presented as being typical and should not be construed to limit the invention unduly.

N 3 oxapentamethylene S tert butylthiosulfenyl dithiocar'oamate, N-pentamethylene-S-tert-butylthiosulfenyl dithiocarbamate, N- tetramethylene-S-tert-butylthiosulfenyl dithiocarbamate, and N-betaphenylethylS-tert-butylthiosulfenyl dithiocarbamate were each prepared by reacting tert-butylthiosulfenyl chloride respectively with (1) sodium 3-oxapentamethylene dithiocarbamate, (2) sodium pentarnethylene dithioearbamate, (3) sodium tetramethylene dithiocarbamate, and (4) sodium N-betaphenylethyl dithiocarbamate, as described hereinafter. In the preparation of the tert-butylthiosulfenyl dithiocarbamate, tert-butyldisulfide and isopentane were charged in proportions of about 900 cc. of isopentane per mol of the disulfide to a reaction flask equipped with a stirrer, thermometer, and a bubbler inlet for admitting chlorine. The reaction flask was partially immersed in a Dry Ice-acetone bath. After flushing the reaction flask with nitrogen, agitation of the isopentane-disulfide mixture was started, and, after the temperature had dropped to -40 chlorine gas was bubbled into the solution through the bubbler inlet. The temperature of the solution was maintained between -40 F. and -50 F. by controlling the flow of chlorine therethrough. One mol of chlorine was introduced into the reaction fiask per mol of disulfide initially charged. After chlorination, the Dry Ice bath was removed and a resulting isopentane solution of tert-butylthiosulfenyl chloride was allowed to warm to about 50 F.

Each of the dithiocarbamate reactants described above was prepared in a reaction flask equipped with a stirrer, a Dry Ice condenser, and a dropping funnel, in an equal molar amount, based on the quantity of tert-butylthiosulfenyl chloride prepared as described'above. In carrying out the preparation of each sodium dithiocarbamate reactant, a per cent excess of sodium hydroxide together with 300 cc. of water per mol of the sodium hydroxide, was charged to the reaction flask. After the sodium hydroxide had dissolved and the solution cooled to room temperature, one mol of an amine (morpholine in the preparation of sodium 3-oxapentamethylene dithiocarbamate; piperidine in the preparation of sodium pentamethylene dithiocarbamate; pyrrolidine in the preparation of sodium tetraamethylene dithiocarba'znate; and beta-phenylethylamine in the preparation of sodium N-betaphenylethyl dithiocarbamate) per mol of the tertiary butylthiosulfenyl chloride prepared, was charged to the reaction flask. An equal molar quantity of carbon disulfide, based on the added amine, was added to the solution in the reaction flask through the dropping funnel during which time that solution was stirred vigorously. Subsequent to addition of the carbon disulfide, the resulting water solution was cooled to room temperature (about 70 F.) and the isopentane solution of tert-butylthiosulfenyl chloride prepared as set forth hereinabove was gradually added to the reaction flask through the dropping funnel. After this addition, the resulting reaction mixture was stirred for about minutes. The water phase and isopentane phase then separated into two layers, and the water phase was discarded. The separated isopentane phase was washed with water and the isopentane was stripped there from by heating the solution to 122 F. at 10 mm. Hg, absolute pressure. The residual product of stripping was an oil phase constituting the desired alkylthiosulfenyl dithiocarbamate product of the reaction. The following tabulation sets forth the products formed in each case, in terms of yield, density and index of refraction:

Oil product recovered We claim:

1. A process for the preparation of an alkylthiosulfenyl dithiocarbamate having a composition in accordance with the structural formula:

i N-C wherein each R is selected from the group consisting of aryl hydrocarbon, aralkyl and alkaryl radicals containing not more than 10 carbon atoms, and radicals which together form a divalent radical selected from the group consisting of pentamethylene, 3-monooxapentamethylone, 3 monoazapentamethylene, 3 monothiapentamethylene, 2 methylpentamethylene, tetramethylene, hexamethylene, Z-methyltetramethylene, 3-methylhexamethylene, 2-ethyltetramethylene, 2-propylhexan1ethylene, said divalent radical forming a heterocyclic ring with the nitrogen, wherein one R, can also be a radical selected from the group consisting of hydrogen, and an alkyl containing not more than 10 carbon atoms, and wherein R. is selected from the group consisting of primary, secondary, and tertiary alkyl radicals, containing not more than 10 carbon atoms, said method comprising reacting an alkylthiosulfenyl halide having a composition in accordance with the structural formula,

R'S-S-X wherein R is as above described, and wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine, with a dithiocarbamate having a composition in accordance with the following structural formula:

wherein each R is as above described and wherein M is selected from the group consisting of alkali and alkaline earth metals.

2. The process of claim 1 wherein said halide is dissolved inan inert organic solvent and is added to an aqueous solution of said dithiocarbamate.

3. The process of claim 2 wherein said solvent has a boiling point within the range of 10 to 40 C. and the reaction is conducted in the refiuxing solvent.

4. The process of claim 3 wherein the reactants are introduced in equi-molar proportions.

5. The process of claim 1 wherein said reacting is effected in a chemically inert organic solvent at a temperature within the range of l0 to 60 C.

6. The process of claim 1 wherein said reacting is eifected by dissolving said halide in an inert organic solvent boiling within the range of 10 to 40 C. and gradually adding the resulting solution to an aqueous solution of said dithiocarbamate under solvent refluxing conditions.

'7. A process for the preparation of 3-oxapentamethylene S tert butylthiosulfenyl dithiocarbamate comprising reacting sodium 3-oxapentamethylene dithiocarbamate with tert-butylthiosulienyl chloride, effecting said reacting by dissolving said tert-butylthiosulfenyl chloride in a chemically inert organic solvent and gradually adding the resulting solution to an aqueous solu-- tion of said sodium 3-oxapentamethylene dithiocarbamate maintained at a temperature within the range of 10 to 40 C., and thereafter recovering 3 oxapentamethylene S tert butylthiosulfenyl dithiocarbarnate product from the resulting reaction mixture.

8. A process for the preparation of pentamethylene S tert butylthiosulfenyl dithiocarbamate comprising reacting sodium pentamethylene dithiocarbamate with tert-butylthiosulienyl chloride, efiecting said reacting by dissolving said tertbutylthiosulienyl chloride in a chemically inert organic solvent and gradually adding-the resulting solution to an aqueous solution of said sodium pentamethylene dithiocarbamate maintained at a temperature within the range of 10 to 20 C., and thereafter recovering pentamethylene-S-tert-butylthiosulfenyl dithiocarbamate product from the resulting reaction mixture.

9. A process for the preparation of tetramethylene S tert butylthiosulfenyl dithiocarbamate comprising reacting sodium tetramethylene dithiocarbamate with tert-butylthiosulfenyl chloride, effecting said reacting by dissolving said tert-butylthiosulfenyl chloride in a chemically inert organic solvent and gradually adding the resulting solution to an aqueous solution of said sodium tetramethylene dithiocarbamate at a temperature within the range of 10 to 40 C., and thereafter recovering tetramethylene S tert butylthiosulfenyl dithiocarbamate product from the resulting reacting mixture.

10. A process for the preparation of N-betaphenylethyl-S-tert-butylthiosulfenyl dithiocarbamate comprising reacting sodium N-betaphenylethyl dithiocarbamate with tert-butylthiosulfenyl chloride, effecting said reacting by dissolving said tert-butylthiosulfenyl chloride in a chemically inert organic solvent and gradually adding the resulting solution to an aqueous solution of said sodium N-beta-phenylethyl dithiocarbamate maintained at a temperature within the range of 10 to 40 C., and thereafter recovering N-beta-phenylethyl-S-tert-butylthiosulfenyl dithiocarbamate product from the resulting reaction mixture.

11. The process of claim 2 wherein said inert organic solvent is a pentane.

12. As a new composition of matter an alkylthiosulfenyl dithiocarbamate having a composition in accordance with the following structural formula:

wherein each R is a radical selected from the group consisting of aryl hydrocarbon, aralkyl and alkaryl radicals containing not more than 10 carbon atoms, and radicals which together form a divalent radical selected from the group consisting of pentamethylene, 3-monooxapentamethylene, 3-monoazapentamethylene, 3-1nonothiapentamethylene, Z-methylpentarnethylene, tetramethylene, hexamethylene, Z-methyltetramethylene, 3-methylhexamethylene, Z-ethyltetramethylene, 2-propylhexamethylene, said divalent radical forming a heterocyclic ring with the nitrogen, wherein one R can also be a radical selected from the group consisting of hydrogen and an alkyl containing not more than 10 carbon atoms, and wherein R is selected from a group consisting of primary, secondary, and tertiary alkyl radicals, containing not more than 10 carbon atoms.

13. A new compound characterized by the structural formula Hz Hg -0 s o N- ss-stertc,m

0-0 H2 H2 14. A new compound characterized by the structural formula 15. A new compound characterized by the structural formula 16. A new compound characterized by the structural formula 17. A new compound characterized by the structural formula 18. A process for the preparation of 3-azapentamethylene-S-tert-butylthiosulfenyl dithiocarbamate comprising reacting an alkali metal 3-azapentamethylene dithiocarbamate with a tert-butylthiosulfenyl halide selected from the group consisting of chloride, bromide and iodide, and recovering 3-azapentamethylene-S-tert-butylthiosulfenyl dithiocarbamate as a product of the process.

19. A process for the preparation of 3-oxapentamethylene-S-tert-butylthiosulfenyl dithiocarbamate which comprises reacting an alkali metal 3 -oxapentamethylene dithiocarbamate with a tert-butyl thiosulfenyl halide selected from the group consisting of chloride, bromide and iodide, and recovering 3-oxapentamethylene-S-tert-butylthiosulfenyl dithiocarbamate as a product of the process.

20. A process for the preparation of pentamethylene-S-tert-butylthiosulfenyl dithiocarbamate which comprises reacting an alkali metal pentamethylene dithiocarbamate with a tert-butylthiosulfenyl halide selected from the group consisting of chloride, bromide and iodide, and recovering pentamethylene-S-tert-buty1thiosulfenyl dithiocarbamate as a product of the process.

21. A process for the preparation of tetramethylene-S-tert-butylthiosulfenyl dithiocarbamate which comprises reacting an alkali metal tetramethylene dithiocarbamate with a tert-butylthiosulfenyl halide selected from the group consisting of chloride, bromide and iodide, and recovering tetramethylene-S-tert-butylthiosulfenyl dithiocarbamate as a product of the process.

22. A process for the preparation of N-betaphenylethyl-Stert-butylthiosulfenyl dithiocarbamate which comprises reacting an alkali metal N-beta-phenylethyl dithiocarbamate with a tertbutylthiosulfenyl halide selected from the group consisting of chloride, bromide and iodide, and recovering N-beta-phenylethyl-Stert-butylthiosulfenyl dithiocarbamate as a product of the process.

23. The process of claim 1 wherein the temperature of said reacting is within the range of -10 to +60 C.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,368,515 Blake Jan. 30, 1945 2,390,713 Hunt Dec. 11, 1945 

12. AS A NEW COMPOSITION OF MATTER AN ALKYLTHIOSULFENYL DITHROCARBAMATE HAVING A COMPOSITION IN ACCORDANCE WITH THE FOLLOWING STRUCTURAL FORMULA: 